3250009-3130/12/4802-0325 �2012 Springer Science+Business Media, Inc.

Key Laboratory of Tropical Crop Biotechnology, Ministry of Agriculture, Institute of Tropic Bioscience andBiotechnology, Chinese Academy of Tropic Agricultural Sciences, Haikou 571101, P. R. China, fax: +86 10 66890978,e-mail: mmpeng_2000@yahoo.com; hfdai2001@yahoo.com.cn. Published in Khimiya Prirodnykh Soedinenii, No. 2, March–April,2012, pp. 291–292. Original article submitted December 29, 2010.

Chemistry of Natural Compounds, Vol. 48, No. 2, May, 2012 [Russian original No. 2, March–April, 2012]

HIGH-LEVEL 1,8-CINEOLE IN THE Alpinia officinarumESSENTIAL OIL FROM HAINAN ISLAND OF CHINA

Jiao Wu, Lu-Wang Lei, Wen-Li Mei, UDC 547.913Hao-Fu Dai,* and Ming Peng*

Alpinia officinarum Hance (also called galanga, galangal, galingale or galangale) is a pungent and aromatic driedrhizome, which has been used as an aromatic stomachic, analgesic, and antiemetic in Asia [1]. Few studies on the oil in therhizome of A. officinarum (small galanga) have been reported. Previous studies showed that 1,8-cineole was the major constituentof the essential oil from small galangal (8.2–50%) and greater galangal (39.4%) [2–7]. The volatile constituents of the driedrhizome of A. officinarum Hance, growing in Dingan County in Hainan Island, of which the major constituent is 1,8-cineole(also called eucalyptol > 70%), is reported for the first time by GC and GC-MS. The essential oil was analyzed using theretention time locked method (www. Agilent.com/chem), and 30 compounds (92.2%) were identified by comparing theirRI with those reported from the literature and mass spectrometric data using Flavor. LIB and NIST08.LIB. Twelve of the30 compounds identified were detected for the first time. These are 3-methyl-2-hexanone, (–)-myrtenol, valeric anhydride,neoclovene, �-humulene, eremophilene, �-selinene, �-calacorene, dendrasaline, nerolidol, cadala-1(10),3,8-triene, andcaryophyllene oxide, as listed in Table 1. It is notable that the oil is rich in 1,8-cineole (72.7%). In addition, 1,8-cineole wasalso the main component of the essential oil from fresh (50.0%) and dried (8.2%) rhizome of galangal in Hanoi, Vietnam [5].

RI: relative to C8-C24 n-alkanes on HP-5 column. Methods of identification: MS, by comparison of the mass spectrum withNIST08.LIB and Flavor. LIB (www. Agilent.com/chem). Tr.: trace quantities (< 0.1%). %: percentage of content (v/w) of eachconsitituent in total volatiles. *Tentative identification based upon mass spectrum and RI only restored by NIST.LIB.

Compound RI % Ref. Compound RI % Ref.

3-Methyl-2-hexanone �-Pinene Camphene �-Pinene 1,8-Cineole Camphor Isoborneol 4-Terpineol �-Terpeneol Piperitol trans-Carveol Myrtenol* Valeric anhydride* Cycloisosativene �-Elemene Caryophyllene �-Bergamotene Neoclovene

843 919 937 974 1044 1146 1147 1159 1170 1182 1204 1206 1282 1366 1392 1421 1439 1451

0.2 0.3 0.4 0.8

72.7 1.5 Tr. 0.2 0.4 1.3 6.4 Tr. 0.2 0.1 0.2 1.2 1.1 0.2

[9] [5] [10] [11] [12] [13] [14] [5] [5] [5] [5]

[15] [5] [16] [5] [17]

�-Humulene Germacrene Eremophilene �-Selinene �-Farnesene �-Calacorene* Dendrasaline Germacrene B Cadala-1(10),3,8-triene Nerolidol Caryophyllene oxide �-Cadinol Monoterpene hydrocarbons Oxygen-containing monoterpenes Sesquiterpene hydrocarbons Oxygen-containing sesquiterpenes Total identified

1457 1479 1490 1499 1516 1546 1557 1559 1564 1568 1587 1618

0.4 0.2 0.7 0.5 0.8 0.3 0.2 0.2 0.1 0.1 1.1 0.4 1.5

82.6 5.6 1.8

92.2

[10] [5]

[18] [19] [5]

[20] [21] [22] [23] [10] [14]

TABLE 1. Volatile Compounds Identified in the Dried Rhizome of Small Galangal in Hainan Island

______

326

The hydrocarbons in the oil were �-pinene (0.3%), camphene (0.4%), and �-pinene (0.8%) as the monoterpene, andcaryophyllene (1.2%), ��-bergamotene (1.1%), and �-farnesene (0.8%) as the major sesquiterpene. Lawrence et al. [1] andLy et al. [5] also reported that the compounds mentioned above were the major components in the fresh rihizome [1, 5]. Theratio of hydrocarbons to oxygenated constituents for the dried sample is obviously higher than that for fresh rhizome in spiteof the reduction of monoterpene hydrocarbons [1]. An important reason may be that eucalyptol, as the major oxygenatedcompound, showed a significant decrease in concentration during drying of the rhizome [5].

There are many processed foodstuffs to which aromatic plants containing different levels of 1,8-cineole and/or theiressential oils may be added as flavorings [8]. So, the essential oil from these plants, of which the major constituent is eucalyptol(> 70%), may be suggested as a new exciting potential source of food additives.

A. officinarum rhizomes in underground dormancy for four years (approx.) were collected from Dingan County ofHainan Island in November 2010. The air-dried rhizome was subjected to steam distillation for 3 h using a Clevenger apparatusto produce the essential oil in a yield of (1.1%, w/w) based on the dry weight.

The GC analysis was carried out using an Agilent GC-7890A equipped with FID using a HP-5 column (30 m � 0.25 mm;0.25 �m film thicknesses). The program was started by a column temperature set at 60�C, increased to 240�C at 3�C/min and held for10 min. Aliquot of oil (1 �L) was injected into the column using a 25:1 split injection, whose temperature was initialized at 250�C.

The GC/MS analyses were performed on an Agilent 7890A gas chromatograph equipped with a split/splitless inlet incombination with Agilent 5975C MSD. Separation was done on a 30 m � 0.25 mm; 0.25 �m HP-5MS column (� = 250) withHe as the carrier gas. The mass spectrometer was operated in the 70 eV EI mode with scanning from 40 to 400 amu.

ACKNOWLEDGMENT

This research was financially supported by the National Nonprofit Institute Research Grant of CATAS-ITBB(No. ITBBZD0741).

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